JP5929654B2 - 強誘電体薄膜形成用組成物及びその薄膜の形成方法 - Google Patents
強誘電体薄膜形成用組成物及びその薄膜の形成方法 Download PDFInfo
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Description
先ず反応容器に、Zrテトラn−ブトキシド(Zr源)と、Tiイソプロポキシド(Ti源)と、乳酸(安定化剤)とを入れて、窒素雰囲気中で還流した。次いでこの化合物に酢酸鉛3水和物(Pb源)と酢酸ランタン1.5水和物(La源)とを添加するとともに、プロピレングリコール(溶剤)を添加し、窒素雰囲気中で還流し、減圧蒸留して、副生成物を除去した後に、この溶液に希釈アルコールを添加することで、各金属比Pb/La/Zr/Tiが125/3/52/48である、酸化物換算で10質量%濃度の金属化合物を含有する組成物1を得た。ここで、乳酸(安定化剤)の混合割合は組成物中の金属合計量1モルに対して2モルである。この組成物1に、組成物1に含まれるPLZT分子100モル%に対し外割で0.1モル%(モノマー換算)のポリビニルピロリドン(重量平均分子量:5000)を添加し、更に副生成物のパーティクルを除去し、この組成物1をスピンコート法により、基板上に塗布して塗膜を形成した後に、この基板上の塗膜を空気中で350℃(塗膜の結晶化温度未満の温度)に加熱して乾燥した。ここで、PLZT分子100モル%はPLZTのAサイト原子100モル%に相当する。また基板は、表面酸化したSi基材上、即ちSi基材表面のSiO2層上に、TiO2層とPt層がこの順に蒸着されたPt層(最上層)/TiO2層/SiO2層/Si基材[Si基材の結晶配向面:(100)面]構造を持つ耐熱性の積層基板であり、上記組成物1をPt層上に塗布した。更に上記塗布工程と上記乾燥工程を所定の回数繰返した後、基板上の塗膜を700℃(塗膜の結晶化温度以上の温度)の酸素雰囲気中でRTA(Rapid Thermal Annealing)熱処理して焼成し、基板上に膜厚180nmの強誘電体薄膜を作製した。この薄膜を実施例1とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で0.1モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で10000、50000及び100000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ実施例2、3及び4とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で0.3モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で5000、10000、50000及び100000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ実施例5、6、7及び8とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で0.5モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で5000、10000、50000及び100000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ実施例9、10、11及び12とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で1.0モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で5000、10000、50000及び100000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ実施例13、14、15及び16とした。
組成物1に、何も添加しなかったこと以外は、実施例1と同様にして基板上に薄膜を作製した。この薄膜を比較例1とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で1.5モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で5000、10000、50000及び100000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ比較例2、3、4及び5とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で0.1モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で3000及び200000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ比較例6及び7とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で0.3モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で3000及び200000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ比較例8及び9とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で0.5モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で3000及び200000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ比較例10及び11とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で1.0モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で3000及び200000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ比較例12及び13とした。
組成物1に、この組成物1に含まれるPLZT分子100モル%に対し外割で1.5モル%(モノマー換算)のポリビニルピロリドンを添加し、その添加量が、重量平均分子量で3000及び200000であること以外は、実施例1と同様にして基板上に薄膜をそれぞれ作製した。これらの薄膜をそれぞれ比較例14及び15とした。
実施例1〜16及び比較例1〜15の薄膜の静電容量及び比誘電率をそれぞれ測定した。具体的には、得られた強誘電体薄膜を形成した基板について、メタルマスクを用い、表面に一辺約250μmの正方形状のPt上部電極をスパッタリング法にて作製し、このPt上部電極と強誘電体薄膜直下のPt下部電極との間におけるC−V特性(静電容量の電圧依存性)を周波数1kHzにて−5V〜5Vの範囲で評価した。また測定された静電容量の最大値より比誘電率を算出した。なお、C−V特性の測定には、精密LCRメータ(ヒューレット・パッカード社(HP社)製、precision LCR meter 4284A)を用いた。また測定条件は、バイアスステップ(bias step)を0.1Vとし、電圧の周波数を1kHzとし、電圧の変動レベル(oscillation level)を30mVとし、遅延時間(delay time)を0.2秒とし、温度を23℃とし、湿度を50±10%とした。その結果を表1に示す。なお、表1には、上記薄膜の静電容量及び比誘電率とともに、組成物1中のPb/La/Zr/Tiの比と、組成物1に添加された安定化剤と、組成物1に添加されたポリビニルピロリドン(PVP)の分子量及び添加量と、薄膜の焼成雰囲気とをそれぞれ示した。
先ず反応容器に、Zrテトラn−ブトキシド(Zr源)と、Tiイソプロポキシド(Ti源)と、乳酸(安定化剤)とを入れて、窒素雰囲気中で還流した。次いでこの化合物に酢酸鉛3水和物(Pb源)を添加するとともに、プロピレングリコール(溶剤)を添加し、窒素雰囲気中で還流し、減圧蒸留して、副生成物を除去した後に、この溶液に希釈アルコールを添加することで、各金属比Pb/La/Zr/Tiが125/0/52/48である、酸化物換算で10質量%濃度の金属化合物を含有する組成物2を得た。ここで、乳酸(安定化剤)の混合割合は組成物中の金属合計量1モルに対して2モルである。この組成物2に、組成物2に含まれるPZT分子100モル%に対し外割で0.3モル%(モノマー換算)のポリビニルピロリドン(重量平均分子量:10000)を添加し、更に副生成物のパーティクルを除去し、この組成物3をスピンコート法により、基板上に塗布して塗膜を形成した後に、この基板上の塗膜を空気中で350℃(塗膜の結晶化温度未満の温度)に加熱して乾燥した。ここで、ここで、PZT分子100モル%はPZTのAサイト原子100モル%に相当する。また基板は、表面酸化したSi基材上、即ちSi基材表面のSiO2層上に、TiO2層とPt層がこの順に蒸着されたPt層(最上層)/TiO2層/SiO2層/Si基材[Si基材の結晶配向面:(100)面]構造を持つ耐熱性の積層基板であり、上記組成物2をPt層上に塗布した。更に上記塗布工程と上記乾燥工程を所定の回数繰返した後、基板上の塗膜を700℃(塗膜の結晶化温度以上の温度)の酸素雰囲気中でRTA(Rapid Thermal Annealing)熱処理して焼成し、基板上に膜厚180nmの強誘電体薄膜を作製した。この薄膜を実施例17とした。
先ず反応容器に、Tiイソプロポキシド(Ti源)と乳酸(安定化剤)とを入れて、窒素雰囲気中で還流した。次いでこの化合物に酢酸鉛3水和物(Pb源)を添加するとともに、プロピレングリコール(溶剤)を添加し、窒素雰囲気中で還流し、減圧蒸留して、副生成物を除去した後に、この溶液に希釈アルコールを添加することで、各金属比Pb/La/Zr/Tiが125/0/0/100である、酸化物換算で10質量%濃度の金属化合物を含有する組成物3を得た。ここで、乳酸(安定化剤)の混合割合は組成物中の金属合計量1モルに対して2モルである。この組成物3に、組成物3に含まれるPT分子100モル%に対し外割で0.3モル%(モノマー換算)のポリビニルピロリドン(重量平均分子量:10000)を添加し、更に副生成物のパーティクルを除去し、この組成物3をスピンコート法により、基板上に塗布して塗膜を形成した後に、この基板上の塗膜を空気中で350℃(塗膜の結晶化温度未満の温度)に加熱して乾燥した。ここで、ここで、PT分子100モル%はPTのAサイト原子100モル%に相当する。また基板は、表面酸化したSi基材上、即ちSi基材表面のSiO2層上に、TiO2層とPt層がこの順に蒸着されたPt層(最上層)/TiO2層/SiO2層/Si基材[Si基材の結晶配向面:(100)面]構造を持つ耐熱性の積層基板であり、上記組成物5をPt層上に塗布した。更に上記塗布工程と上記乾燥工程を所定の回数繰返した後、基板上の塗膜を700℃(塗膜の結晶化温度以上の温度)の酸素雰囲気中でRTA(Rapid Thermal Annealing)熱処理して焼成し、基板上に膜厚180nmの強誘電体薄膜を作製した。この薄膜を実施例18とした。
Claims (8)
- チタン酸鉛系ペロブスカイト膜又はチタン酸ジルコン酸鉛系複合ペロブスカイト膜からなる強誘電体薄膜を形成するための強誘電体薄膜形成用組成物において、
前記組成物が、酢酸鉛と、乳酸からなる安定化剤と、ポリビニルピロリドンとを含み、
前記組成物に含まれるペロブスカイトAサイト原子に対するモノマー換算した前記ポリビニルピロリドンのモル比が0を超え0.015未満であって、
前記ポリビニルピロリドンの重量平均分子量が5000以上100000以下である
ことを特徴とする強誘電体薄膜形成用組成物。 - 前記チタン酸鉛系ペロブスカイト膜又は前記チタン酸ジルコン酸鉛系複合ペロブスカイト膜が一般式[(PbxLay)(ZrzTi(1-z))O3]で示される請求項1記載の強誘電体薄膜形成用組成物。
ここで、前記一般式において、0.9<x<1.3、0≦y<0.1、0≦z<0.9である。 - 前記チタン酸鉛系ペロブスカイト膜又は前記チタン酸ジルコン酸鉛系複合ペロブスカイト膜を構成するための原料は、有機基がその酸素原子又は窒素原子を介して金属元素と結合している化合物である請求項1記載の強誘電体薄膜形成用組成物。
- 前記チタン酸鉛系ペロブスカイト膜又は前記チタン酸ジルコン酸鉛系複合ペロブスカイト膜を構成するための原料は、有機酸塩、金属アルコキシド、金属β−ジケトネート錯体、金属β−ジケトエステル錯体、金属β−イミノケト錯体、及び金属アミノ錯体からなる群より選ばれた1種又は2種以上である請求項3記載の強誘電体薄膜形成用組成物。
- 前記安定化剤が、前記組成物中の金属合計量1モルに対して0.2〜3モルの割合で更に含まれる請求項1ないし4いずれか1項に記載の強誘電体薄膜形成用組成物。
- 前記組成物に含まれるペロブスカイトAサイト原子に対するモノマー換算した前記ポリビニルピロリドンのモル比が0.001以上0.01以下である請求項1記載の強誘電体薄膜形成用組成物。
- 請求項1ないし6いずれか1項に記載の強誘電体薄膜形成用組成物を基板に塗布して塗膜を形成する塗布工程と、前記基板に形成された塗膜を、空気中、酸化雰囲気中又は含水蒸気雰囲気中で加熱して乾燥する乾燥工程と、
前記乾燥工程の途中から或いは完了後に前記塗膜を、O2,N2,Ar,N2O,H2若しくはこれらの混合ガス中又は乾燥空気中或いは水蒸気を含む前記雰囲気中で結晶化温度以上で焼成する焼成工程と
を含む強誘電体薄膜の形成方法。 - 請求項1ないし6いずれか1項に記載の強誘電体薄膜形成用組成物を基板に塗布して塗膜を形成する塗布工程と、前記基板に形成された塗膜を、空気中、酸化雰囲気中又は含水蒸気雰囲気中で加熱して乾燥する乾燥工程と、
前記塗布工程及び前記乾燥工程を複数回繰返す繰返し工程と、
前記繰返し工程の最終乾燥工程の途中から或いは完了後に前記塗膜を、O2,N2,Ar,N2O,H2若しくはこれらの混合ガス中又は乾燥空気中或いは水蒸気を含む前記雰囲気中で結晶化温度以上で焼成する焼成工程と
を含む強誘電体薄膜の形成方法。
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